稻壳基二氧化硅/碳复合材料的表面改性及对天然橡胶的影响

doi:10.7503/cjcu20190077

摘要/Abstract

摘要：

以稻壳基二氧化硅/碳复合材料(SiCB)作为天然橡胶(NR)的补强填料, 采用表面化学改性的方法将天然乳胶(NRL)接枝到SiCB表面, 改善其与NR基体的相容性. 研究了不同处理方法对接枝NRL效率的影响, 以及填料填入NR后对硫化橡胶力学性能的影响. 结果表明, 经过硝酸和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(γ-MPTMS)预处理, NRL能高效接枝在SiCB表面, 得到的样品SiCB_MR10比未处理的SiCB_P有更强的补强能力. 硫化胶NR/SiCB_MR10的拉伸强度、 300%定伸和撕裂强度较NR/SiCB_P分别提高了61.06%, 27.15%和15.90%, 与传统炭黑产品N774填充的硫化胶NR/N774的力学性能相近. 经过NRL接枝改性的SiCB_MR10具有替代商业炭黑的应用前景.

关键词: 二氧化硅/碳复合材料, 表面改性, 天然乳胶, 力学性能

Abstract:

Surface modification of silica/carbon black(SiCB) derived from rice husks was carried out by grafting with natural rubber latex(NRL). The effect of different pre-treatments on the grafting efficiency was investigated and the mechanical properties of NR/NRL-grafted SiCB vulcanizates were tested. The results indicated that the SiCB pre-treated by nitric acid and 3-(trimethoxysilyl) propyl methacrylate(γ-MPTMS) can be effectively grafted with NRL via the strong interfacial bonding. The above modified SiCB(SiCB_MR10) exhibited good dispersion state and superior reinforcement ability, attributed to the use of NRL as a compatibilizer for filler-matrix composites. The tensile strength, stress at 300% elongation and tear strength of NR/SiCB_MR10 were 61.06%, 27.15% and 15.90% higher than those of NR/SiCB_P, respectively. The modified SiCB_MR10 achieved the similar reinforcement with the conventional carbon black(N774) in mechanical properties of NR vulcanizate. The results showed that SiCB_MR10 exhibited an ideal reinforcing effect on rubber.

Key words: Silica/carbon black composite, Surface modification, Natural rubber latex, Mechanical property

中图分类号:

O636
O611.4

TrendMD:

隋佳烊, 刘晓旸, 钱苗苗, 朱燕超, 薛北辰, 丰祎, 田玉美, 王晓峰. 稻壳基二氧化硅/碳复合材料的表面改性及对天然橡胶的影响. 高等学校化学学报, 2019, 40(7): 1561.

SUI Jiayang, LIU Xiaoyang, QIAN Miaomiao, ZHU Yanchao, XUE Beichen, FENG Yi, TIAN Yumei, WANG Xiaofeng. Surface Modification of Silica/carbon Black Derived from Rice Husks and Its Influence on Natural Rubber Composites^†. Chem. J. Chinese Universities, 2019, 40(7): 1561.

图/表 12

Scheme 1 Preparation flow diagram of the NRL-grafted SiCB samples * Quality rate of NRL(or BPO) to SiCB.

Table 1 NR/SiCB compound formulations

Material	m/g	Material	m/g
NR	100.0	4010NA	1.8
Filler^*	50.0	Antioxidant RD	1.0
Stearic acid	2.5	Antioxidant H	0.3
Zinc oxide	5.0	NOBS	0.7
Paraffin	1.0	Sulfur	2.3
Aromatic oil	6.0

Fig.1 FTIR spectra of SiCBP(A), SiCBSI(B), SiCBA(C) and SiCBM(D)

Fig.2 TEM images of SiCBP(A), SiCBPR10(B), SiCBSIR10(C) and SiCBMR10(D)

Fig.3 SEM images of SiCBP(A), SiCBPR10(B), SiCBSIR10(C) and SiCBMR10(D)

Fig.4 Grafting efﬁciency of SiCBPR10, SiCBSIR10 and SiCBMR10

Scheme 2 Preparation mechanism of SiCBMR10

Fig.5 Water static contact angles of SiCBPR10(A), SiCBSIR10(B) and SiCBMR10(C)

Fig.6 Static precipitation of SiCBP, SiCBPR10, SiCBSIR10 and SiCBMR10 after 1 min(A), 2 h(B), 8 h(C), 10 h(D) and 15 d(E)

Fig.7 SEM images of tensile fractured surfaces of NR/SiCBP(A), NR/SiCBPR10(B), NR/SiCBSIR10(C) and NR/SiCBMR10(D)

Table 2 Mechanical properties of NR/SiCB composites and the NR/N774 composite

Sample	Tensile strength/MPa	Elongation at break(%)	Stress at 300% elongation/MPa	Tear strength/ (kN·m^-1)	Shore A hardness
NR/N774	18.35	1226.27	4.02	44.76	57.00
NR/SiCB_P	13.38	919.56	3.72	38.29	57.00
NR/SiCB_PR10	15.69	1456.52	2.95	35.40	53.00
NR/SiCB_SIR10	16.58	1494.03	2.91	38.12	52.00
NR/SiCB_MR10	21.55	1166.61	4.73	44.38	56.00

Fig.8 Akron abrasion of the rubber compositesa. N774; b. SiCBP; c. SiCBPR10; d. SiCBSIR10; e. SiCBMR10.

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